Azo dyestuffs



Patented Mar. 17, 1936 UNITED STATES 2,034,668 PATENT OFFICE AZODYESTUFFS N. Y., a corporation of Delaware No Drawing. Application March22, 1932, Serial No. 600,561. In Germany March 26, 1931 14 Claims. (01.260-79) v The present invention relates to new azo dyestufis and processof producing the same.

We have found that valuable azo dyestufis are obtained by coupling thediazo compound of an aromatic amine with a coupling component containingin its molecule an aliphatic radicle of at least 10 carbon atoms.Coupling components which may be used for the purpose of our invention,comprise amino and hydroxy derival tives of aromatic compoundscontaining the said aliphatic radicle attached-directly to the nucleus,or by means of a linking member, for example an oxygen atom, or a or a--SO2O group and preferably by means of the imino group NH or theacylamino groups 20 -NHCO- or NHSO'.-. Suitable coupling components are,thereforeyamino and hydroxy compounds of aralkyls, ethers, esters,imines and acylamines. Any kind of coupling components hitherto employedin the prepara- 25, tion of azo dyestufis may be used provided theycontain the said aliphatic radicle attached. Thus, also couplingcomponents substituted by, the most various kinds of substituents may beemployed, for example they may contain halo- 30 gen atoms or alkyl,alkoxy, aralkyl, nitro, carboxylic and, in particular, sulphonic acidgroups. The said coupling components containing an aliphatic radicle ofat least carbon atoms may be prepared according to customary methods, 35for example by condensation of aromatic polyamines or amino hydroxycompounds with aliphatic acids containing the-said number of carbonatoms or halides thereof, for example capric, lauric, myristic,palmitic, margaric, stearic, ara- 4 chidic and like fatty acids, orunsaturated acids, such as oleic, erucic, elaidic, linoleic acid and theacids present in soja bean oil, or the halides, in particular thechlorides, of the said acids. Coupling components containing thealiphatic 45 radicle attached by means of an oxygen atom may be preparedby condensation of aromatic hydroxy compounds with alcoholscorresponding to the aforesaid acids which may be prepared by reductionof the acids. Other aliphatic 50 alcohols containing the said number ofcarbon atoms may, of course, be used as well, for example cetyl'alcohol.In a similar manner coupling components containing the aliphatic radicleattached by means of a carboxylic group are obtained by condensation ofan aromatic aminoor hydroxy-carboxylic or sulphonic acid with theaforesaid alcohols. Imines may be prepared by condensation of aromaticamines with an alcohol containing at least 10 carbon atoms 60 with theaid of hydrochloric acid as condensing iast to washing.

agent. They may also be produced by condensing the alkyl chloridescorresponding to the aforesaid alcoholswith aromatic amines.

On the other side the newazo dyestufis can be derived from any diazocomponent hitherto 6 employed, for example such as are obtained frommonoor poly-amino derivatives of aromatic compounds, for example suchderived from benzene or naphthalene and its homologues, aralkyl,hydroxy, alkoxy, halogen, nitro, carboxylic and 10 sulphonic acidderivatives. Further, there may be employed amino derivatives ofdiphenyl, benzophenone, diphenylsulphone, diphenyl urea,diphenyleneketone, carba'zole, diphenylmethane, diphenylether, stilbene,azobenzene and many others and the aforesaid substitution productsthereof. All azo dyestufis prepared from the aforesaid components havedistinct advantages over those hitherto known which reside in case ofwater-insoluble azo dyestufis in their good solubility in organicsolvents which makes them particularly suitable for coloring lacquers orartificial-masses, such as celluloid and the like. The azo dyestufiswhich are water-soluble due to the presence of sulphonic or carboxylicacid groups, are particularly suitable for dyeing in view of the goodfastness to washing and fulling of the dyeings.

The following examples will further illustrate the nature of thisinvention but the invention is not restricted thereto. The parts are byweight.

Example 1 12.7 parts of meta-chloraniline are diazotized in the usualmanner and coupled with 34 parts of the condensation product from lauricacid chloride and 1,8-aminonaphthol-4,6-disulphonic acid in a solutionrendered alkaline with soda.

A bluish red dyestufi is obtained which dyes wool very fast shades.

After having been laked with barium chloride, the dyestufi may alsobeemployed as a lake yestufl.

Example 2 17.3 parts of metanilic acid are diazotized in the usualmanner and coupled with 61 parts of the condensation product fromstearic acid chloride and 1,8-aminonaphthol-3,6-disulphonic acid in asolution rendered alkaline with soda. A dyestuif is obtained which dyeswool red shades Example 3 30.3 parts of 1-naphthylamine-5,7-disulphonicacid are diazotized in the usual manner and introduced into an alkalinesolution of 49 parts of para-aminostearlc acid anilide of acetoaceticacid which may be obtained by'the condensation of para-aminostearlc acidanilide with acetoacetic ester. Adyestuflisobteinedwhichdyeawool yelloworange shades fast to washing and falling.

Example 4 28 parts of dodecylaniline arecoupled in acid solution with25.3 parts of diaaotined 2,4-aniline disulphonic acid. A dyestufl isobtained which dyes wool intense yellow shades of very good lastness towashing and iulling.

Example 5 A bluishreddyeingproductiaobtainadintbe 'aforedescribed mannerfrom dialotiaed aniline.

Example 6 24.4 parts of dianisidine are tetranotined in'the usual mannerand coupled with 122 parts of the condensation product employedaccording to Example 5 in a solution rendered alkaline by means ofsodium carbonate. A dyestun' is obtained dyeing wool from an acid bathblue shades of good i'astness to washing and iulling. The iastness tolight oi. the dyeings may be improved by treating the dyestufl insubstance or in the dye-bath with copper salts.

Unsymmetrical diazo dyestufls can of course be prepared fromtetrazotized benzidine or dianisidine, these dyestufls having the samegood propertles.

In the following table a number of diazo dyestuiis obtainable accordingto the present invention and their dyeing properties are described:

Diem component First coupling component Second coupling component Shadgg i on Dianiaidine Condensation product 0! oleic acid chlo-Condensetion product oi oleic acid chlo- Blu ride with limlno-shydrory-naphtharide with l-amino-8hydroxy-nephthalens-3,6-disulphonicacid lene-3,6-dishlphonic acid Dianiaidine Condensation product oioleicacid chloride Condensation product oioleic acid chloride Blue violetwith Zamino-S-hydroxy-naphthalene-G- with2-amino-8-hydroxy-naphthulene6- sulphonic acid sulphonic acid 1Dianisidine Con ensation product of oleic acid chloride Condensationproduct oi cieic acid chloride Reddish blue with1-amino&hydroxy-naphthalene-7- with l-amino-5-hydroxy-naphthalene-7- sulhonic acid sulphonic acid Dianisidine Con ensation product 0! stearicacid chlo- Condensation product of steeric acid chlo- Blue ride withl-aminp-8-hydroxy-naphtharide withl-amlno-8-hydroxy-naphthalone-3,6-disuiphonrc acid lene-3,6-disulphonicacid Dianisidine Con ensation product oi oleic acid chlorideCondensation product oi oleic acid chloride Blue withl-anlino-s-hydrory-naphthalenewith 2-emino5-hydroxy-naphthaiene-7-ii-disulphonic acid sulphonic acid Dianisidine. Condensation productoioleic acid chloride 2, 5, 7-auiinonaphthol sulphonic acid Reddish bluewith l-amino-B-hydroxy-naphthalene- 3,6-dlsulphonic acid DianisidlneCondensation product ololeic acid chloride2-phenylimino-S-hydroxy-naphthalene-l- Reddish blue withi-amiuo-ii-hydrow-nephthalenecarboxylic acid 3,6-drsulphomc acidDianlsidine. Condensation product oioleic acid chloride 2,8-nephtholsulphonic acid Blue {ith l-amino-B-hydmxy-naphthalene- DianisidineCondensation prodnctololeic acid chloride Condensation productsaiieylic-sulpho Reddish blue with 1-amino-8-hydrexy-naphthalenechloride and Z-methylimino-S-hydroxy- 3,6-disulphonic acidnaphthalene-7-sulphonic acid Dianiaidine Condensation product oi oleicacid chloride 3-methyl-l-phenyl-5-pyrazolone repared Reddish blue withl-amino-8-hydroxy-naphthalenafrom 2-amino4-hydroxy-dip enylsul- 3,o-disulphonic acid phone-4, 3"-sulpho-carboxylic acid of the formulagiven at the end at the table Dianisidiue Condensation productoioleicacid chloride 2,8- dihydrory-nephthalene -e-sulphonic Beddieh blue 4alzflyddroxy-napththaleneacid Dianisidine Condensation productol'oleicecid chloride 1,4-naphtholsulphonic acid. Reddish blue withl-amino-8-h naphthalene- 3,6-disuiphonic Dianisidine .2 Condensationproductoioleicecid chloride a-methyl-l-phenyl-opyrarolone Blue withl-amino-snaphthalene- 3,6-disulphomcac 'lolidine Condensation product oioleic acid chloride Condensationproduct oi oleic acid chloride Reddishblue with 1-amino-8- ydroxy-naphthalenewithl-ammo-B-hydroxy-napththalene- 3,6-disulphoinc acid 3,6-disulphouic acidTolidine- Con ensation product oi'oieic acid chloride2,6-naphtholsulphonic acid Blue violet vith l-allliino-s-hydroxy-naphthalene- ,o-disulp omcacid Benzidine-o-disulphonioacid- Condensation mt oioloio acid chloride Condensation product ofoleic acid chloride Brick red.

with o-ii-hydroxy-naphthalenewith 2-amino-5-hydroxy-naphthalenev7-sulphouic acid. 7-sulphouic acid.

Diamino-benzophenone Condensation product oi'oleic acid chlorideCondensation product oi'oleic acid chloride Reddish violet.

with 1-amino-8-hydmxy-naphthaleuewith l-amino-B-hydmxy-naphthalene-3,6-d1sulphonic acid 3,6-disulphonic acid Diamiuo-benzophenoneCondensation product oioleicacid chloride 2,6-naphtholsulphonic acid--.Red

- p with l-amino-B- -naphthalene- 3,6-disulphonic Diamino-benzophenoneCondensation productoioleicacid chloride ii-methyl-l-phenyl-o-pyrazoloneRed idio s m'iia o Diamino-benzophenone Condensation product oioleicacid chloride 1-(p-sulphophenyl)-5#pyrazolone-3-carbox- RedgtfigQa-Igrmr-B-hydmxy-nephthaleneylic acid I P 0 c MDiamino-benzophenone Condensation product oioleic acid chloridel-(2-hydrory-3'-earboxy-5'-sulphophenyl)- Red withl-amino-s-hydroxy-naphthalene 3-methyl-5-pyrazolone 8,6-disulphonic acidI Diamino-benzophenone. Condensation product oi oleic acid chloridel-phenyl-5-pyrazolone-3-carboxylic acid.-- Red with 1-amino-8-hydroxynaphthaiene 3,6-disulphonic acid.

Toiidine-m-disulphonio acid Condensation product of oleic acid chlorideCondensation product oi oieic acid chloride Bluish red with$amino-8-hydroxynaphthalene-6- with 2-amino-8-hydroxynaphthalene-6- v;aulfhonic acid sul honic acid Tolidine-m-disulphonio acid. Con ensationproduct oi oleic acid chloride Con eusation product oi oleic acidchloride Brick red with Z-amino-G-hydroxynaphthalene-7- with2-amino-5-hydroxynaphthalene-7- sulphonic acid sulphonic acid Example 737 parts of the monoazodvestufl's from diazotizedl-naphthylamino-B-sulphonic acid and o:- naphthylamine are diazotized'inthe usual manner in a hydrochloric acid solution by means 01' '7parts of sodium nitrite and coupled with 62 parts of a solution of thecondensation product described in Example 5 in a solution containing anexcess of sodium carbonate. A dyestufl is obtained dyeing wool from anacetic acid bath fast blue violet shades.

A dyestufi of practically the same properties is obtained in theaforedescribed manner by replacing the said condensation productDreparedby means of stearicchloride instead of oleic chloride, thusshowing that the kind of the aliphatic radicle present, generallyspeaking, has no great influence on'the shade of the dyestuif.

Example 8 30 parts of 5-amino-2-benzoylamlno-l,4 -hydroquinone-diethylether are diazotized and coupled with 62 parts of the condensationproduct described in Example 5. A dyestuil is obtained dyeing wool veryfast clear greenish blue shades.

The dyestufi obtained'in an analogous manner when using diazoti'zed3-amino-4-methoxy-6- benzoylamino-l-methyl benzene as diazo component isvery similar to the aforedescribed dyestufi but yields more reddishshades.

Example 10 25.2 parts of diazotized 2.4-.aniline disulphonic acid arecoupled in an alkaline solution with 40 parts of2-hydronaphthalene-6-sulpho dodecylamide. A dyestufi is obtained dyeingwool red shades of good fastness to washing and fulling.

EmmplelI 30.1 parts of 1,3,6-naphthylamine disulphonic acid arediazotized in the usual manner and coupled with 32 parts of4-methyle3-laurylamidophenol in pyridine rendered alkaline. A dyestuilis obtained dyeing wool orange shades of very good fastness properties.

Example 12 17.2 parts of metanilic acid are diazotized and coupled in analkaline. solution with about 32 parts of 1,4naphthohydroquinonemonodecyl ether. A blue red dyeing dyestufi is thusobtained.

Eaample 13 20.4 parts of para-aminosulphosalicylic acid(COOH:OH:NH22SO:H=1:2:5:3) are diazotized and coupled with 39 parts ofthe dodecylester of 2,3-hydroxynaphthoic acid in an alkaline solution.The dyestufl thus obtained dyes wool fast red shades which may still beimproved as regards fastness to light by aiter-chroming.

Example 14 9.3 parts of aniline are diazotized and coupled ina solutioncontaining pyridinewith 40 parts of'1-hydroxynaphthalene-4-sulphododecylamide A red dyestufi is obtainedwhich is readily soluble in organic solvents.

What we claim is:-

1; Azo dyestuils corresponding to the general formula I YR-N=NR'X 1 inwhich R stands for an aromatic radicle, R for the radicle of a couplingcomponent containing a benzene or naphthalene nucleus, X for analiphatic radicle containing at least 10 carbon atoms which is attachedto R either directly or by means of a linking member selected from thegroup consisting of and Y stands for hydrogen or for the group R"N=N-,wherein R" is a benzene or naphthalene radicle, saiddyestuils containingat least in which R stands for an aromatic radicle, R for the radicle ofa coupling component containing a benzene or naphthalene nucleus and Xfor an aliphatic radicle containing at least 10 carbon atoms which isattached to Rf either directly or by means of a linking member selectedfrom the. group consisting of the said dyestufis containing at least onesubstituent selected from the class consisting of the carboxylic andsulphonic acid group and being obtainable by coupling a diazotizedarcmatic amine with a coupling component of the benzene or naphthaleneseries containing the said aliphatic radicle attached thereto, at leastone of the said components containing at least one substituent selectedfrom the class consisting of the carboxylic and sulphonic acid groups.

3. Azo dyestufis corresponding to the general formula:

in which R stands for an aromatic radicle, R'

' for a naphthalene radicle and X for an aliphatic radicle containing atleast 10 carbon atoms which is attached to R either directly or by meansof 4 a Making member-selected from the group consisting of in which Rstands for an aromatic radicle, R for a naphthol radicle and x for analiphatic radicle containing at least carbon atoms which is attached toR. either directly or by means of a linking member selected iroin thegroup con-' sisting r the said dyestuffs containing at least onesubstituent selected irom the class consisting of the earboiqrlic andsulphonic acid groups and being obtained by coupling a diazotizedaromatic amine with a naphthol coupling component containing the saidaliphatic radicle attached thereto, at least one of the said componentscontain-w ing at least one substituent selected irom the classconsisting of the carboxylic and sulphonic acid groups.

5. Azo dyestuffs corresponding to the general formula:

in which R standsior an aromatic radicle, R fora naphthol sulphonic acidradicle and x for an aliphatic radicle containing at least 10carbonatoms which is attached to R either directly or by means of alinking member selected from the group consisting of the said dyestufiscontaining at least one. substituent selected from the class consistingoi the carboxylic and sulphonic acid groups and being obtained bycoupling a diazotized aromatic amine with a naphthol sulphonic acidcoupling com-' ponent containing the said aliphatic radicle attacheglthereto.

6. A zo dyestuffs corresponding to the general i a i in which It standsfor a diphenyl radicle, R. for anaphthoI radicle, X-ior analiphaticradicle containing at least 10 carbon'atoms which is attached to R.either directly or by means of a linki gmember selected irom the groupcon sisting of and R for an aromatic radicle, the said dyestufl'scontaining at least one substituent selected from the classconsistingoithe carboxylic and sulphonic acid groups and being obtained by couplinga tetrazotized -benzidine with an aromatic coupling aosaeea .t

containim the said aliphatic radicle attached thereto, at least one oithe said components containing at least one substituent selected fromthe class conslsting oi the carboxylic and sulphonic acid groups.

'1. Aso dyestuil's p nding to the general i'ormula: k i

on NB! whereinnstandsiortheradicleoiadiazotiaed aromatic amine. 9.Water-soluble aao the general iormula in which It stands for the radicalof "a diazotized aromatic amine, R for a benzene or a naphthaleneradical, and x for an aliphatic radical containlng-at least 10 carbonatoms, said dyestuils dyestuilfs corresponding to containing a groupselected from the class con-' sisting oi sulionic and carboxylic acidgroups.

' 10. Ana dyestuiifs corresponding to the general i'ormula v in which Rstands for the radical of a diazotized aromatic amine, R for a benzeneor a naphtha.- lene radical, and x for an-aliphatic radical containingat least 10 carbon atoms, said dyestuil's containing a group selectedfrom the class consisting of sultonic and carboxylic acid groups in theradical R.

ll. Water-soluble azo dyestuffs corresponding to the general formula inwhich R stands for the radical of a diazotized aromatic amine, R for abenzene or naphthalene radical and Xior an aliphatic radical containingat least 10 carbon atoms, which is at!- tached to R by a group selectedfrom the class consisting of v corresponding to thegeneral in which Itstands for the radical of a diazotized aromatic amine, R for a benzeneor naphthalene radical and X for an aliphatic radical contain- 7 5component and a naphthol coupling component ing at least 10 carbonatoms. which is attached wherein R for the radicle of a diazotized o,-co, -so,0,-Nn, NHCO-and NHso,, said dyestuffs containing a. groupselected from the class consisting of sulfonic and carboxylic acidgroups in the radical R.

- 13. A water-soluble azo dyestufi' comprising an aromatic diazocomponent coupled to a coupling component consisting of 1,8-aminonaphtho1-3, 6-disulfonic acid having an H atom in the amino groupsubstituted by an aliphatic 'acyl radical containing at least 10 carbonatoms.

a,os4,ces 5 to R by a 'group selected from the class con- 14. Azodyestufis corresponding to the general sisting of formula:

HANS REINDEL. HANS KRZIKALLA. WALTER LIMBACHER.

